US5663469A - Production of vinylidene olefins - Google Patents
Production of vinylidene olefins Download PDFInfo
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- US5663469A US5663469A US08/596,812 US59681296A US5663469A US 5663469 A US5663469 A US 5663469A US 59681296 A US59681296 A US 59681296A US 5663469 A US5663469 A US 5663469A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/30—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
Definitions
- This invention relates to an improved process enabling the production of vinylidene olefins in good yields with high selectivities.
- Vinylidene olefin which are branched monoolefins having the structure (R 1 )(R 2 )C ⁇ CH 2 where R 1 and R 2 are the same or, more usually, different alkyl groups, are of commercial importance as raw materials for use in producing-double tailed oxo alcohols and other functionalized derivatives, used in the manufacture of detergents, surfactants, specialty agricultural chemicals, and fuel or lubricant additives.
- Vinylidene olefins can be produced by dimerizing vinyl olefins.
- U.S. Pat. No. 4,155,946 to Sato, Noguchi and Yasui discloses a process for dimerizing lower ⁇ -olefins in which the catalyst system is formed from (1) a trialkylaluminum compound, (2) a salt or complex of nickel, (3) a trivalent phosphorus compound selected from specified groups, and (4) a halogenated phenol.
- U.S. Pat. No. 4,709,112 to Sato, Ikimi, Tojima and Takahashi describes a process for dimerizing lower ⁇ -olefins which uses a catalyst system formed from (1) a trialkylaluminum compound, (2) an organic salt or complex of nickel, (3) a trivalent phosphorus compound selected from specified groups, (4) a fluorinated isopropanol, and (5) a catalyst co-activator selected from specified types of halogenated compounds.
- U.S. Pat. No. 4,973,788 to Lin, Nelson and Lanier describes a process for dimerizing a vinyl olefin monomer at a selectivity of at least 85 mol percent. This is accomplished by use of a catalyst which consists essentially of 0.001-0.04 mols of trialkylaluminum per mol of vinyl olefin, and conducting the reaction at a temperature in the range of about 100°-140° C. for a time sufficient to convert at least 80 mol percent of the initial vinyl olefin to a different product.
- the reaction rate under these conditions is quite slow, and thus a long reaction time is required. For example it is pointed out that the time required for 90 percent conversion at 120° C.
- the vinylidene dimerization reaction with a trialkylaluminum catalyst involves the catalytic interaction (perhaps transitory coupling) between the vinyl olefin and the aluminum alkyl.
- the dimerization is effected at temperatures of 100°-140° C. It has now been found that at these and higher temperatures, isomerization of vinyl olefin to internal olefin can occur. This competitive reaction reduces dimerization product yield, because these isomers do not further react to produce the desired vinylidene olefin product.
- isomerization of linear 1-olefins is known to occur when trace amounts of certain metals, especially nickel, react with the aluminum alkyl catalysts.
- certain metals especially nickel
- Ziegler et at. Justus Liebigs Ann. Chem. Volume 629 at pages 25 and 62 (1960) mentioned using phenyl acetylene to reduce isomerization in olefin displacement reactions catalyzed by nickel.
- the present invention has accomplished this goal, and made it possible to achieve all of these highly beneficial results.
- Another embodiment of this invention is a process which comprises (a) charging a reaction vessel with vinyl olefin and at least one trialkylaluminum compound as dimerization catalyst in a ratio in the range of 0.001 to 0.5 mol of trialkylaluminum per mol of the initial vinyl olefin, and (b) heating the mixture at one or more temperatures in the range of about 100° to about 200° C.
- the liquid mixture is maintained in direct contact with a nickel-containing metal alloy surface for at least one hour at a temperature above about 50° C., and that at least one acetylenic hydrocarbon is added to the mixture prior to said contact in an amount at least sufficient to inhibit double bond isomerization in the reaction mixture but insufficient to inhibit formation of the vinylidene dimer.
- the amount of acetylenic hydrocarbon added to the reaction mixture is at least sufficient to overcome the deleterious effect of the nickel present on dimer selectivity.
- this invention represents the first time consideration has been focused upon the interrelationships among reaction conditions, materials of construction, and competitive reaction rates in the conduct of an olefin dimerization process.
- vinyl olefin when a vinyl olefin is heated in the presence of a trialkylaluminum dimerization catalyst to a temperature at which dimerization takes place, competitive reactions can and generally do occur.
- vinyl olefin in addition to the desired dimer formation via the Markovnikov route, vinyl olefin can be also be dimerized to deep internal olefin dimer via the competitive anti-Markovnikov route.
- vinyl olefin can be isomerized to internal isomer olefin via aluminum hydride route or by other known mechanisms.
- this invention also makes it possible to overcome the dire consequences on dimer selectivity resulting from the presence of nickel impurities that may be present as impurities in one or more materials fed to the reactor, and/or that may be present as residues or other types of contamination in the reactor or in auxiliaries, such as storage vessels, pumps, feed lines, agitators, valves, and the like.
- Another feature of this invention is that although aluminum to hydrogen bonds serve as catalysts for isomerization of a 1-olefin to an internal olefin, and although the rate at which trialkylaluminum compounds dissociate into olefin and dialkylaluminum hydride rapidly increases with increasing temperature, the process of this invention enables the formation of vinylidene olefin products of almost as high a purity as the process of U.S. Pat. No. 4,973,788 in much shorter reaction periods.
- Still another feature of the process of this invention is that it takes advantage of the exothermic nature of the olefin dimerization reaction.
- the heat of reaction is about 20 Kcal per g mol of dimer formed.
- One such mode involves use of a single reactor commonly referred to as a "stirred pot reactor" in which the reaction is conducted with agitation on a batch basis.
- the reactor comprises at least two closed vessels in which the reaction is conducted with agitation and continuous feed, the vessels being connected in series such that the feed rate to the first vessel, and the discharge rates from each vessel to the ensuing vessel, where there is an ensuing vessel, are substantially equal to each other.
- the third mode utilizes a single continuous elongated reactor in which the reaction is conducted with agitation on a continuous basis.
- the vapor space in the reactor is in the range of 0 to 40 percent (more preferably in the range of 5 to 25 percent) of the total interior free space of the reactor, and
- the reaction is most preferably conducted such that during at least 50 percent of the time that the reaction mixture is at a temperature above about 110° C. in one or more of the vessels:
- the vapor space in such vessels is in the range of 0 to 40 percent of the total interior free space of the vessels
- k is a rate constant which is a function of temperature, and is in terms of liters per gram mol per hour;
- [alR] is the molar concentration of aluminum alkyl
- X is vinyl olefin conversion as defined by the expression:
- Vi ⁇ is the vinyl olefin molar concentration at time t.
- [Vi ⁇ o is the initial vinyl olefin molar concentration.
- the vinyl olefins used in the process can be one or more linear vinyl olefins or one or more branched chain vinyl olefins or any mixture of these. Minor amounts of internal and/or vinylidene monoolefins (e.g., up to 40 mol % of an olefin mixture) can be present in the initial vinyl olefin charged to the reactor. The amount of such internal and/or vinylidene olefins, if any, is of course excluded from consideration when calculating the mol ratios of catalyst to initial vinyl olefin used in the process. Typically the vinyl olefins used in the process will contain in the range of about 3 to about 30 or more carbon atoms per molecule.
- the initial vinyl olefin will contain in the range of 6 to 20, and still more preferably in the range of 8 to 16 carbon atoms per molecule.
- a substantially pure single vinyl olefin such as 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, or 1-tetradecene.
- mixtures of vinyl olefins are entirely suitable. In such case co-dimerization (a special case of dimerization) takes place.
- any trialkylaluminum compound can be used as the sole catalytic component charged to the dimerization reaction zone in the practice of this invention.
- the alkyl groups will contain from 1 to 30 carbon atoms, and preferably in the range of 2 to about 18 carbon atoms each.
- trialkylaluminum compounds in which substantially all of the alkyl groups are a straight chain primary alkyl groups having in the range of from 2 to about 14 carbon atoms, such as triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tris(decyl)aluminum, tris(tetradecyl)aluminum, and the like.
- the hydride content, if any, of the aluminum trialkyl should be quite low, e.g., the aluminum trialkyl should have a maximum aluminum hydride equivalent of not more than about 0.8%
- the aluminum trialkyl as fed to the process is essentially hydride-free, i.e., the trialkylaluminum product contains, if any, a maximum of 0.10 wt % of aluminum hydride equivalent, and more preferably a maximum of 0.05 wt % of aluminum hydride equivalent, because the aluminum hydride bond can cause isomerization of 1-olefins to internal olefins.
- the one or more acetylenic hydrocarbons introduced into the reaction mixture before it is exposed to a nickel-containing metal surface at a temperature above about 50° C. can be a straight chain compound such as 1-hexyne or 2-hexyne, or a branched chain compound such as 4-methyl-1-pentyne or 5-methyl-1-hexyne, or a mixture or combination thereof. Any aliphatic, cycloalphatic or aromatic hydrocarbon having an acetylenic group may be suitable, especially if it has an immediately adjacent carbon atom that is substituted by two or three hydrogen atoms.
- the acetylenic hydrocarbon is a straight chain alkyne having from 4 to about 10 carbon atoms in the molecule, such as 1-butyne, 2-butyne, 1-pentyne, 2-pentyne, 1-hexyne, 2-hexyne, 3-hexyne, 1-heptyne, 2-heptyne, 3-heptyne, 1-octyne, 2-octyne, 3-octyne, 4-octyne, and analogous nonynes and decynes. Mixtures of such alkynes having the same or different number of carbon atoms in the molecule can also be used.
- Hexyne has been found to be highly effective when added at low dosage levels in suppressing double bond isomerization without inhibiting dimerization. Moreover, since it is a liquid at room temperatures is easy to handle and dispense to the reaction mixture. Moreover, its low molecular weight means that for a given weight fraction, more mols of hexyne are present in the system than with larger molecules such as phenylacetylene. Also, unlike phenylacetylene, hexyne is non-carcinogenic.
- the alkyne must be used in conjunction with the trialkylaluminum compound. That is, experimental work has shown that the alkyne is incapable of complexing or otherwise passivating the nickel in the absence of the trialkylaluminum compound. The mechanism by which the alkyne effects passivation of the nickel or otherwise overcomes the devastating effect nickel can have on dimer selectivity in the process is not known.
- the effective nickel-passivation amounts of the alkyne hydrocarbon can be quite small, and will depend in large measure to the amount of nickel contamination to be encountered in the hot reaction mixture. In any given situation it is desirable to perform a few pilot experiments to determine the amount of alkyne that overcomes the adverse effect of the nickel that can be introduced into the reaction mixture by contact with nickel-containing surfaces, especially at elevated temperatures. Generally speaking, the amount used pursuant to this invention is enough to result in a dimer selectivity that is not more than 3 wt% (preferably not more than 2 wt%) less than the dimer selectivity achieved under absolutely identical conditions in a clean glass-lined reactor with the sole exception that in reaction performed in the glass-lined reactor, no alkyne is added.
- the amount of alkyne used will give a dimer selectivity at least equal to, if not greater than, the dimer selectivity in the reaction performed in identical fashion (without alkyne addition) in the glass-lined reactor.
- the amount introduced at the appropriate stage of the operation will not exceed about 5000 ppm (wt), and typically amounts in the range of up to about 2500 ppm are used.
- the smaller the amount sufficient to effectively inhibit double bond isomerization during dimerization the better, as this minimizes costs and maximizes product purity.
- any amount which provides the passivation under the conditions at hand without adversely affecting the dimer selectivity and vinylidene purity in any material way can be used.
- the dimerization is conducted predominately (more than half of the reaction period) at one or more temperatures in the range of about 120° to about 180° C., more preferably in the range of above 140° to about 180° C., such as in the range of 160° to 170° C., in all such cases with reaction periods in the range of 1 to 24 hours sufficient to convert at least 10% (preferably at least 50% and more preferably at least 80%) by weight of the initial vinyl olefin to a different product. Reaction periods longer than 24 hours can be used, but are distinctly less desirable in a commercial operation.
- a particularly preferred embodiment involves conducting the dimerization predominately at temperatures in the range of about 165° ⁇ 3° C. with reaction periods in the range of about 6 to about 12 hours sufficient to convert at least 85% by weight of the initial vinyl olefin to a different product.
- the reaction should be conducted in an environment that is essentially anhydrous and substantially free of oxygen and air.
- Aluminum trialkyls can react violently with water or compounds containing hydroxyl groups such as alcohols. Thus even a small amount of water, alcohol, or the like, in the system will inactivate some of the aluminum trialkyl.
- the amount of aluminum alkyl catalyst can be increased to compensate for the water or other active hydrogen component such as alcohol whereby the proper amount of active aluminum trialkyl catalyst remains in the system even after part of the initial aluminum alkyl has been destroyed by the water or other active hydrogen compound.
- the olefin feed can be pretreated to remove water or alcohol contamination.
- the process should be conducted under a dry inert atmosphere e.g., nitrogen, argon, neon, or the like, to prevent catalyst destruction.
- the temperature of the reactor heating medium at (or close to) the desired reaction temperature. Both heat from the heating medium and heat of reaction are utilized to bring the reaction mixture from room temperature to the reaction temperature. When the reactor temperature is higher than the temperature of the heating medium, the heat transfer direction will be reversed, i.e., from reaction mixture to the heating medium.
- the same heating medium at almost the same temperature may be used both as the heating medium during heat up to reaction temperature, and, as the cooling medium if and when the reaction temperature is passed. Either stem or other heating media such as Dowtherm may be used.
- the liquid mixture is maintained in direct contact with a nickel-containing metal alloy surface for at least one hour at a temperature above about 50° C., and at least one acetylenic hydrocarbon is added to the mixture prior to the time such contact occurs, the amount added being at least sufficient to inhibit nickel-induced double bond isomerization in the reaction mixture but insufficient to inhibit formation of the vinylidene dimer.
- the acetylenic hydrocarbon can be added to the mixture in any of a variety of ways.
- the acetylenic hydrocarbon can be added to the vinyl olefin before the vinyl olefin is charged into the reactor and in this case the acetylenic hydrocarbon is carried into the reactor with the vinyl olefin before or at the same time the mixing with the trialkylaluminum compound occurs.
- the acetylenic hydrocarbon can be added to the trialkylaluminum compound before the trialkylaluminum compound is charged into the reactor and in this case the acetylenic hydrocarbon is carried into the reactor with the trialkylaluminum compound before or at the same time the mixing with the vinyl olefin occurs.
- the mixture formed by the combining of the vinyl olefin, the trialkylaluminum and the acetylenic compound is maintained in at least one reactor in direct contact with steel alloy interior surfaces, especially nickel-containing steel alloy surfaces, for at least a major portion of the total period of time (and preferably all of the time) during which such reaction mixture is at a temperature above about 50° C.
- a passivating amount of an acetylenic hydrocarbon is included in a mixture formed by combining vinyl olefin and trialkylaluminum in a ratio in the range of 0.001 to 0.5 mol of trialkylaluminum per mol of the initial vinyl olefin, and at a temperature below about 50° C. (most preferably at ambient temperatures below about 30° C.), to form a dimerization feed mixture which (a) contains a nickel impurity and/or (b) will be exposed before or during dimerization to at least one nickel-containing surface when at a temperature above about 50° C. for a time sufficient in the absence of the inclusion said acetylenic hydrocarbon to result in double bond isomerization and loss of dimer selectivity during dimerization; and
- the dimerization mixture is heated at one or more temperatures in the range of about 100° to about 200° C. for a period of time sufficient to convert from 10 to about 99% by weight of the initial vinyl olefin to a different product with at least 80 % vinylidene dimer selectivity.
- the passivating amount of the acetylenic hydrocarbon will usually be up to about 5000 parts by weight per million parts by weight of the mixture and, in any event, is at least sufficient to result in a dimer selectivity that is not more than 3 wt% less (preferably not more than 2% less, and more preferably not more than 1% less) then the dimer selectivity achieved under identical conditions in a clean glass-lined reactor and with no detectable nickel present either in the feed or in the reaction mixture.
- the concentration of nickel impurity present in a reaction mixture sufficient to cause undesirable isomerization and loss of dimer selectivity at dimerization reaction temperatures in the range of 120° C. or above is about 2 or 3 ppm (wt) or less, and can be as little as 1 ppm or less.
- suitable nickel-containing steels for use in fabricating the reactor are the so-called mild steels and low-alloy steels, as long as such steels do not contain so much nickel that 5000 ppm of the acetylenic hydrocarbon is incapable of suppressing double bond isomerization to no more 0.5 wt% more than the percentage by weight of double bond isomerized product formed under identical conditions in a scrupulously clean glass-lined reactor of identical interior volume using the same quantities of the same vinyl olefin and of the same trialkylaluminum compound in the absence of the acetylenic hydrocarbon.
- the steel or other metal alloy to which the reaction mixtures of this invention are exposed has been passivated by treatment with air or oxygen.
- the fresh (i.e., thoroughly clean) nickel-containing steel or alloy surfaces of the reactor and auxiliaries feed lines, valves, stirrer parts, baffles, or the like
- auxiliaries feed lines, valves, stirrer parts, baffles, or the like
- portions of the overall reaction system or train with which the feed and/or reaction mixture comes in contact when at temperatures of 50° C. or above can be composed of suitable materials other than nickel-containing steels or nickel alloys.
- suitable materials include glass (e.g., glass-lining), nickel-free steels, and mild metals such as copper.
- this invention makes it possible to use nickel-containing reactors and/or auxiliaries in a dimerization process without experiencing the devastating consequences on dimer selectivity that can result from exposure of the dimerization reaction mixture to non-passivated nickel-containing surfaces at elevated dimerization reaction temperatures. Also, the dire consequences of nickel-containing impurities in the feeds to the dimerization reaction can also be overcome by the practice of this invention.
- any surface contamination such as previous reaction residues from the reactor surfaces, as well as other portions of the reaction system that come in contact with the feeds and/or reaction mixture.
- any surface residues containing significant quantities of nickel should be thoroughly removed from contaminated surfaces.
- metal impurities in or on surfaces that contact the reactor feed or contents such as Na, Li, etc. may also enhance isomerization of vinyl olefins and should also be removed or, preferably, totally avoided wherever possible.
- the reactor Prior to feed transfer to the dimerization reactor, the reactor should be cleaned with aqueous and/or organic solvents.
- the pre-reaction cleanup procedures may include some of the following steps: A) Caustic or acidic wash; B) Water wash; C) Drying (removal of water); D) Heptane (or other heavy paraffin/olefin) wash; and E) Drying (removal of heptane or other heavy paraffin/olefin.)
- Caustic or acidic washing may introduce trace amount of impurities either from the solution or from leaching of material from the interior reactor surfaces. Therefore it is desirable to avoid use of caustic or acidic washing of reactor surfaces. In cases where hot organic solvent wash alone is sufficient to clean up the reactor, aqueous wash is not needed. But in cases where aqueous wash is needed to accomplish the reactor cleanup, use of steam cleaning or hot water wash without use of base or acid is preferred.
- Caustic or acidic wash should only be used if the other alternatives are inadequate in any given
- the reactor history is such that caustic or acidic wash is needed, this should be followed with fresh water washes several times until the quality of final washed water is the same as (or close to) the fresh water used. This may be accomplished by measuring pH or ionic strength (such as Ni, Na, Cl etc.). Since trace amounts of isomerization promoters can reduce dimer yield tremendously, the purest water available at the plant site (e.g., deionized water or distilled water) is preferably used. After water wash is complete and the final wash water is discharged, the reactor should be blown to dryness with by nitrogen, as any residual water in the reactor will destroy the corresponding amount of aluminum alkyl catalyst.
- pH or ionic strength such as Ni, Na, Cl etc.
- organic solvent wash (heptane or others) should follow. Hot heptane wash for several hours under agitation conditions can expedite the organic wash process.
- the reactor is preferably purged with nitrogen to dry the reactor. Nitrogen purge with some heat in the reactor accelerates the heptane drying process.
- metal surface passivation is to be effected by use of air (or oxygen), the cleaned reactor and associated metallic equipment with which the feeds and reaction mixtures come in contact are exposed to air for at least 0.5 hour, preferably for from 0.5 to 3 hours at a temperature of at least about 20° C., such as ambient room temperature up to about 100° C. Shorter exposure periods can be used when employing pure oxygen for surface passivation.
- the dimerization reactor should be maintained with 10 psig N 2 at room temperature. All further processing is performed under a blanket of dry inert gas, preferably a nitrogen blanket.
- the feed transfer lines should be treated with the same diligence as the reactor pretreatment procedure to ensure that no contamination of feeds occurs from the transfer lines.
- a blank isomerization operation This involves charging the reactor under a N 2 blanket or purge with vinyl olefin feed of the type to be used for dimerization. In the absence of trialkylaluminum catalyst; the olefin feed is then heated to 165° C. and kept at that temperature for about 12 hours.
- Such a blank isomerization test makes it possible to determine if there is any isomerization activity in the system in the absence of the trialkylaluminum catalyst. Pilot plant experience has indicated that there isomerization in the above glass-lined reactor during the blank isomerization test even if coupons of carbon steel and/or stainless steel coupons are present in the reactor.
- a blank isomerization test can be also carried out with the hot heavy olefin during the reactor cleanup.
- the reactor must pass a blank isomerization test before proceeding to dimerization. If it does not, the reactor can be cooked for another 24-48 hours using the same olefin to remove any residual materials which may not be completely removed during the reactor pretreatment. Then another blank isomerization test should be conducted using another fresh charge of the olefin feed. If this blank isomerization test still fails, further investigation is required to determine the cause. In this connection, failure in a blank isomerization test is deemed to be the formation in the olefin of 0.5% by weight or more of internal olefin as determined by NMR.
- the specified amount of trialkylaluminum is charged and mixed with the vinyl olefin in the reactor containing 90 wt% of the specified total amount olefin feed to be used in the reaction. Then the remaining amount of vinyl olefin (10 wt% of specified total olefin feed) is charged to flush out any trialkylaluminum which may be trapped in the feed transfer line.
- the specified quantity of alkyne hydrocarbon is introduced before, during or after the trialkylaluminum is charged.
- a preferred series of process steps includes: A) Batch dimerization; B) Caustic wash; C) Phase separation; and D) Distillation. These steps are briefly discussed below.
- Batch dimerization is most preferably carried out at 165° C. using substantially pure linear alpha-olefin (LAO) as the vinyl olefin feed and a charge of triethylaluminum (TEA) (preferably a low hydride grade) as the catalyst.
- LAO substantially pure linear alpha-olefin
- TEA triethylaluminum
- reaction under these conditions typically achieves 90% LAO conversion in 12 hours reaction time.
- an alpha-olefin e.g., 1-octene
- TEA will be converted at least in part to trialkylaluminum in which the alkyl groups correspond to the alpha-olefin (in this example, to tri-n-octyl aluminum).
- the feed charge is such that at reaction temperature, the liquid phase occupies at least 70%, more preferably over 80%, still more preferably 90% or more, and most preferably at least about 95% or more, of the internal reactor volume.
- the catalyst can be, and preferably is, recovered from the reaction product and recycled to the dimerization reactor.
Abstract
Description
X=1-exp{-k[alR]t}
1-[Vi]/[Vi].sub.o
TABLE 1 ______________________________________ Run Dimer Selectivity, No. Pre-Reaction Procedure % ______________________________________ 1 8 ppm Ni added 1.8 2 Heptane wash 3.8 3 Heptane wash 5.8 4 Heptane wash 7.7 5 HCl and Heptane washes 27.1 6 HCl and Heptane washes 57.8 ______________________________________
TABLE 2 ______________________________________ Run Dimer Selectivity, No. Pre-Reaction Procedure % ______________________________________ 7 8 ppm Ni & 160 ppm hexyne added 0.5 8 Heptane wash; 160 ppm hexyne added 61.4 9 Heptane wash; 160 ppm hexyne added 78.5 ______________________________________
TABLE 3 ______________________________________ Run Dimer Selectivity, No. Pre-Reaction Procedure % ______________________________________ 10 8 ppm Ni & 1000 ppm hexyne added 0.9 11 Heptane wash; 1000 ppm hexyne added 88.7 ______________________________________
Claims (36)
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/596,812 US5663469A (en) | 1996-02-05 | 1996-02-05 | Production of vinylidene olefins |
ZA9700870A ZA97870B (en) | 1996-02-05 | 1997-02-03 | Production of vinylidene olefins. |
EP97904156A EP0880486A1 (en) | 1996-02-05 | 1997-02-04 | Production of vinylidene olefins |
PCT/US1997/001624 WO1997028109A1 (en) | 1996-02-05 | 1997-02-04 | Production of vinylidene olefins |
CA002245589A CA2245589A1 (en) | 1996-02-05 | 1997-02-04 | Production of vinylidene olefins |
JP52786797A JP3892044B2 (en) | 1996-02-05 | 1997-02-04 | Production of vinylidene olefins |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US08/596,812 US5663469A (en) | 1996-02-05 | 1996-02-05 | Production of vinylidene olefins |
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US5663469A true US5663469A (en) | 1997-09-02 |
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US08/596,812 Expired - Fee Related US5663469A (en) | 1996-02-05 | 1996-02-05 | Production of vinylidene olefins |
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US (1) | US5663469A (en) |
EP (1) | EP0880486A1 (en) |
JP (1) | JP3892044B2 (en) |
CA (1) | CA2245589A1 (en) |
WO (1) | WO1997028109A1 (en) |
ZA (1) | ZA97870B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6756514B1 (en) | 2002-12-09 | 2004-06-29 | Bp Corporation North America Inc. | Integrated dimerization process |
Citations (6)
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US4155946A (en) * | 1977-06-29 | 1979-05-22 | Sumitomo Chemical Company, Limited | Process for dimerizing lower alpha-olefins |
US4709112A (en) * | 1986-01-06 | 1987-11-24 | Sumitomo Chemical Company, Limited | Process for dimerizing lower α-olefins |
US4795851A (en) * | 1987-03-12 | 1989-01-03 | Uop Inc. | Process for the oligomerization of olefins and a catalyst thereof |
US4973788A (en) * | 1989-05-05 | 1990-11-27 | Ethyl Corporation | Vinylidene dimer process |
US5124465A (en) * | 1991-03-25 | 1992-06-23 | Ethyl Corporation | Aluminum alkyls and linear 1-olefins from internal olefins |
US5516958A (en) * | 1993-12-14 | 1996-05-14 | Albemarle Corporation | Preparation of α, ω-diene oligomers and derivatives thereof |
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1996
- 1996-02-05 US US08/596,812 patent/US5663469A/en not_active Expired - Fee Related
-
1997
- 1997-02-03 ZA ZA9700870A patent/ZA97870B/en unknown
- 1997-02-04 JP JP52786797A patent/JP3892044B2/en not_active Expired - Fee Related
- 1997-02-04 EP EP97904156A patent/EP0880486A1/en not_active Withdrawn
- 1997-02-04 WO PCT/US1997/001624 patent/WO1997028109A1/en not_active Application Discontinuation
- 1997-02-04 CA CA002245589A patent/CA2245589A1/en not_active Abandoned
Patent Citations (6)
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Also Published As
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WO1997028109A1 (en) | 1997-08-07 |
JP3892044B2 (en) | 2007-03-14 |
EP0880486A1 (en) | 1998-12-02 |
CA2245589A1 (en) | 1997-08-07 |
JP2000504671A (en) | 2000-04-18 |
ZA97870B (en) | 1997-08-04 |
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